Zur Rolle von EDA‐Komplexen bei kationischen Polymerisationen. VIII. Zur Charge‐Transfer‐Wechselwirkung von bπ‐Donatoren mit organischen Kationen in Lösung

Abstract

On the Role of EDA‐complexes in Cationic Polymerization. VIII. The Charge‐Transfer‐Interaction of bπ‐Donors with Organic Cations in Solution The interaction of 25 aromatic bπ‐donors with organic cations of the type (RC 6 H 4 ) 3 C ⊕ X ⊖ (R = CH 3 , C(CH 3 ) 3 , OCH 3 , H, Cl, I, NO 2 ; X = BF 4 ⊖ , AsF 6 ⊖ , SbCl 6 ⊖ , FeCl 4 ⊖ ) is investigated by means of u.v.‐spectroscopy. The influence of the dissociation on the charge transfer energy will be discussed. With the decreasing concentration of the salt the charge transfer band is hardly shifted at longer wave length. The charge transfer energy can be described as a linear function of structural parameters (i.e. σ p of R; I p of the donor and reciprocal radius of the anions, respectively). The influence of the solvent is dependent on both the donicity and dielectric factors.